Reactor assembly

ABSTRACT

A reactor assembly for analysing the effluent stream from at least one flow-through reactor, The reactor includes a flow-through reactor for performing at least one chemical reaction. The flow-through reactor includes a reaction chamber including a reaction zone, the reaction chamber being connected to a reactor inlet for a reactant, upstream of the reaction zone and a reactor outlet for the effluent stream from the reaction zone, downstream of the reaction zone; and an analyser for subjecting the effluent stream to an analysing procedure, each reactor outlet being connected to an analyser by an effluent conduit. The reactor assembly further includes a dilution fluid supply member for adding a dilution fluid to the effluent stream, downstream of the reaction zone.

FIELD OF THE INVENTION

The invention relates to a reactor assembly for analysing the effluentstream from at least one flow-through reactor. The invention furtherrelates to a process for analysing a fluid effluent stream from aflow-through reactor.

BACKGROUND OF THE INVENTION

Reactor assemblies are known in the art for e.g. testing optimalreaction conditions for chemical reactions, including biological andpharmacological processes, such as testing the pharmacological activityof a test compound, the activity of a catalyst or enzyme, optimalreaction parameters etc. E.g. WO 99/64160 (herein incorporated byreference) describes a reactor assembly of the above-mentioned kind fortesting and/or screening a collection of compounds in order to find theoptimal reaction conditions and performance of the said compounds. Asthe reactor assembly is designed for testing and or screening purposesand not for production purposes, the reactor outlets are connected to ananalyser, wherein the effluent stream from the reactor is analysed.

In practice, many different analysers are used for testing and/orscreening purposes, such as a gas chromatograph (GC), chromatographydevices, such as chromatography columns, in particular high-performanceliquid chromatography (HPLC), optical defraction measuring devices, massspectrograph, etc.

For testing and/or screening purposes, the reactor assemblies are chosento be as small as possible in size in view of saving material to betested, energy, etc. However, numerous problems often occur when usingreactor assemblies known in the art. When e.g. the composition of areaction mixture is to be analysed, the composition of the effluent ofthe reaction zone is analysed and compared to the composition of thestream entering the reaction zone, e.g. after and before the reaction,respectively. To accurately assess the reaction performance, e.g. theexact mass balance of the in- and outgoing components are to becalculated. Especially when analysing a small amount of effluent stream,in particular when operating with a liquid flow rate of less than 1.0ml/min/reactor, in particular less than 0.5 ml/min, and/or a gas flowrate of less than 100 Nml/min/reactor, in particular less than 50Nml/min/reactor as is often the case in so called high-throughputexperimentation as described in WO 99/64160, it has been proven to bevery difficult to analyse the composition of the effluent stream in anaccurate manner. The term “Nml” means the volume of the gas at 1 atm and20° C. The accuracy of the analyses tends to be more difficult whensmaller amounts of effluent stream are available for analyses. It hase.g. been found that a significant amount of effluent stream may remainin the reaction chamber, e.g. due to adhesion of one or more of thecomponents, present in the effluent stream, to the wall of the reactionchamber, leading to measurement inaccuracies. Further this may alsocause an undesired time delay between the moment the efficient streamleaves the reaction zone and the moment the reactants of the said steamarrive at an analyser, which is highly undesired for high-throughputexperimentation. Further, it is not possible to conduct accuratemeasurements on e.g. concentration, fluxes and production rate when asmall amount of effluent stream is available for analyses.

A particular problem occurs when dealing with gas/liquid mixturesexiting the reactor, especially when dealing with the low flow rates asmentioned above. Gas/liquid separation, which is essential forsubsequent analysis of both phases, is very difficult on the small flowsto be separated. The reason behind this is the fact that a gas liquidseparator for these small flows has to be small as well to avoidunnecessary hold-up of the products to be analysed. The small dimensionsof such G/L separators will cause adhesive forces such as capillaryforce and surface tension effects to dominate over gravity, and as suchwill hinder easy separation based on gravity.

OBJECTS OF THE INVENTION

The main object of the invention is to provide a solution to one or moreof the above and other problems and, among other things, to provide areactor assembly for ensuring that substantially the whole effluentstream can be diluted and prepared for analysis, especially whenoperating with a liquid flow regime of less than 1.0 ml/min, inparticular less than 0.5 ml/min, and/or a gas flow rate of less 100Nml/min/reactor, preferably less than 50 Nml/min/reactor.

SUMMARY OF THE INVENTION

The invention provides reactor assembly having at least one dilutionfluid supply means, for adding at least one dilution fluid to theeffluent stream, downstream of the reaction zone.

By providing dilution fluid supply means, dilution fluid can be added tothe effluent stream, therewith diluting the components of the effluentstream in the dilution fluid, so that sufficient volume, comprising thecomponents of the effluent stream, for accurate analyses procedures ase.g. indicated above is provided.

As indicated above, the reaction chamber accommodates the reaction zone,wherein the chemical reaction takes place. It is to be noted that thechamber may also comprise a first space upstream of the reaction zone,e.g. to allow proper mixing and/or evaporation of reactants, enteringthe reaction chamber from one or more reactor inlets. In the said space,one ore more mixing devices may be present. Further, the reactionchamber may, in presence or absence of the said first space, comprise asecond space downstream of the reaction zone, for receiving the reactionmixture, passing the reaction zone. However, it is also possible thatthe reaction zone occupies the complete reaction chamber.

It is preferred that the complete effluent stream is diluted with thedilution fluid; thereto, the dilution fluid supply means are designedsuch, that the whole effluent stream leaving the reaction zone receivesdilution fluid; the skilled person will be aware of proper positioningof the dilution fluid supply means to dilute the said whole effluentstream. It is particularly preferred that the dilution supply meansdischarge in the reaction chamber, downstream of the reaction zone.

In a preferred embodiment, when the reaction chamber comprises a secondspace, downstream of the reaction zone as described above, the dilutionfluid supply means discharge in the reaction chamber, downstream of thereaction zone, e.g. in the said second space. By such an arrangement,the dilution fluid is contacted with the complete effluent stream,comprising the reaction mixture, ensuring proper dilution of the saidcomplete reaction mixture.

It is preferred to contact the effluent stream with the dilution fluiddirectly after leaving of the effluent stream from the reaction zone.Thereto the dilution fluid supply means preferably discharge in thevicinity of the downstream end of the reaction zone, preferably suchthat the dilution fluid contacts the said downstream end, so that anyloss or delay of components from the reaction mixture is minimised.

In another embodiment, the dilution fluid supply means are connected toeach of the effluent conduits. The reaction chamber can comprise one ormore effluent conduits, each being connected to at least one analyser.As it is preferred to analyse the effluent in each analyser in dilutedform, each of the effluent conduits are capable to receive dilutionsupply means. However, it may also be possible with the assemblyaccording to the invention to provide dilution fluid to one or moreeffluent conduits, while other effluent conduits are present,wherethrough a portion of the effluent stream is transported, e.g. to ananalyser, in undiluted form. With the assembly it will also be able todose more than one diluent fluid to the reactor outlet or effluentconduit(s). The addition of such a multitude of fluids will allowdilution of the reaction products in one of the diluents. Typically themultitude of diluents will be mutually immiscible and form separatephases when coming together, such as for example a gas and a liquidphase. Also two immiscible liquid diluents may be added.

Each reactor preferably has a single reactor outlet, for passing throughthe complete effluent stream. In this case, a single effluent conduit isconnected to the said outlet. Thus, the complete effluent stream istransported through the said single effluent conduit, to one or moreanalysers. In such an arrangement, it is sufficient for the dilutionfluid supply means to be connected to the said single effluent conduit,enabling simple design of the reactor assembly. It is to be understoodhowever, that once the effluent stream is diluted, the effluent conduit,downstream of the entry of the dilution fluid, may be branched, whereinthe conduit branchs can be connected to a plurality of differentanalysers. Also, one or more of the said conduit branches can beconnected to storage or waist vessels in order to respectively store thediluted reaction mixture for later analyses, or to discharge therespective portion of the deluted reaction products.

To get a proper mixing between the effluent and the dilutent a mixingsystem may be placed downstream from the location where the dilutionfluid supply means discharge in the reaction chamber or the effluentconduit(s). Also a buffer vessel may be present to dampen fluctuationsin concentrations that may be caused due to fluctuations in the flow ofthe effluent exiting the reactor.

Preferably, the reaction zone comprises a fixed catalyst bed. The fixedcatalyst bed will at least be part of, or define the reaction zone, whenthe reaction process requires the action of the catalyst in the bed. Bythe fixed bed arrangement, a well-defined reaction zone (the bed) ispresent in the reaction chamber, enabling accurate and optimalpositioning of the discharge end of the dilution supply means within thereaction chamber, i.e. in the vicinity of the downstream end of thecatalyst bed to enable direct dilution of the reaction mixture afterleaving the said catalyst bed. Further, fixed catalyst beds areextremely well suited for testing of or screening for the activity of acatalyst. Preferred is a fixed catalyst bed operating in downflowoperation mode where either or both liquid and gas are following thedirection of gravity. However, also other fixed bed reactor operationmode can be used, such as, counter current, horizontal flow orco-current upflow operation mode. Instead of a fixed catalyst bed alsofluidised bed, ebullating bed, continuously stirred tank reactor or abubble column can be used. In the reaction zone various types ofreactions can be performed, such as, oxidation reactions, hydrogenationreactions, condensation reactions, hydration reactions, de-hydrationreactions and cracking reactions. These reactions may be carried out inthe gas phase, in the liquid phase, or in multi-phase where both gas andliquid reactants are brought in the reaction zone. In case a catalyst ispresent in the reaction zone it may be in the form of e.g. grains (sievefraction), flakes, balls, monoliths or fibres. The catalyst bed can besupported by a frit, a quarts wool plug or a filter plate. Those who areskilled in the art will understand that many more variations can be madeto the above mentioned descriptions of the reaction zone and that manymore reactions can be carried out in that zone.

One of the other advantages of using a fixed catalyst bed reactor forcatalyst testing and/or screening is the fact that the products arecontinuously separated from the catalyst. This allows an easy evaluationand optimisation of process parameters, without having to change out thecatalyst after each change of conditions.

As outlined above, the reactor assemblies for testing and/or screeningpurposes preferably comprise a flow-through reactor of minimal size;thereto, the reaction chamber is preferably of elongated shape having adiameter of at most 5 cm, preferably at most 2 cm, more preferably atmost 1 cm, most preferably having a diameter of 1.7-2.5 mm wherein achemical reaction in a very small volume with small amounts of reactantsand optionally one or more catalysts are possible.

In a preferred embodiment, the dilution fluid(s) supply means dischargein the reactor assembly within at most 10 mm from the downstream end ofthe reaction zone. In case the reaction zone occupies the reactionchamber in full, the said dilution fluid supply means discharge in theeffluent conduit(s) at a distance of at most 10 mm from the reactoroutlet. In case the reaction chamber comprises a second space downstreamof the reaction zone, the dilution fluid supply means discharge openingis preferably at most 10 mm from the downstream end of the said reactionzone, such as the downstream end of a fixed catalyst bed. Such adistance, in particular when the reaction chamber has the aboveidentified shape and diameter, ensures proper dilution of the reactionmixture, substantially without any hold-up of compounds of the saidmixture.

In the reaction zone, gaseous and liquid components can be formed at thereaction conditions used. A gas/liquid mixture often leads tomeasurement inaccuracies, e.g. by the formation of a slug of gas,followed by a slug of liquid in the effluent stream, resulting inpressure variation in the stream and a non-constant flow thereof,leading to measurement inaccuracies. Further, another problem, caused bythe presence of gas in a liquid effluent stream is the fact that liquidanalysers, such as GC or HPLC systems cannot properly be used whengas-bubbles are present in the liquid stream. Gas-bubbles will cause avariation of the amount of liquid injected in such systems. Further, thepresence of gas in the inlet capillary of a mass spectrograph will causestrong measurements fluctuations and also, spectroscopic techniques,such as Ultraviolet-Visible spectroscopy, Near Infrared spectroscopy orInfrared spectroscopy will strongly suffer from light scattering andliquid displacement because of the presence of gas. Further, for propertesting/screening, the determination of the production rate of gaseouscompounds as well as of liquid compounds and quantification thereof isnecessary for accurate analyses of the reaction process. It is thereforhighly advantageous to separate the liquid and the gaseous components inthe effluent stream from each other before being transferred to ananalyser. An additional advantage of the invention is the fact that dueto the addition of diluent the volume of the effluent stream isconsiderably increased. This will allow the use of G/L separators withlarger internal dimensions without causing unnecessary hold-up of theproducts. Thus, the effluent conduit preferably comprises a gas/liquidseparator, therewith enabling proper separation of the gaseous andliquid components from one another, so that the gaseous phase can beanalysed independently from the liquid phase. It is however alsopossible to discard either one of the said phases and to analyse thenot-discarded phase. In some cases it is necessary to add a gas/liquidseparator before discharging the effluent to an analyser. This is thecase when the reactor effluent consists of a gas and a liquid phase, butalso will be necessary when the reactor effluent consists of only liquidand a gas diluent is added, or when the reactor effluent consists ofonly gas and a liquid diluent is added.

The gas/liquid separator will have at least two outlets, onepredominantly containing gas and one predominantly containing liquid,each discharging to a separate analyser. The efficiency of the gasliquid separator is strongly dependent on its size. As the volume offluid is increased by the addition of diluent, as described in thepresent invention, it allows the use of a larger gas/liquid separatorthus increasing its efficiency.

In order to quantitatively analyse the gaseous or liquid stream, it isof importance that the gas/liquid separator is capable of completelyseparate the gaseous from the liquid flow. However, such a separationrequires high sophisticated gas/liquid separator equipment. In a veryattractive embodiment of the present invention, at least two gas/liquidseparators are present in the effluent stream, arranged to one anotherin a serial fashion. In the first upstream separator, a representativeamount of either gas or liquid is separated from the remaining effluentstream, that still may comprise a mixture of both gas and liquid. Theseparated gas or liquid can then be analysed accordingly. In the second,downstream gas/liquid separator, a gaseous flow is separated in case inthe first separator liquid was separated or, when in the first separatorgas was separated, liquid will be separated in the second gas/liquidseparated, possibly leaving a stream still containing gas and liquideffluent leaving the separator. In this way, both gaseous and liquideffluent components can be properly analysed, without the need ofsophisticated gas/liquid separation devices. Such devices may in thisarrangement be of more simple design, as full separation of gas andliquid is not required. Any not separated gas/liquid mixture can bediscarded. Analysis and quantification of the compounds of the effluentstream are preferably performed by incorporation, in the effluentstream, of an internal standard, preferably comprising both a liquid anda gaseous internal standard (see below).

Preferably, the analyser is chosen from the group, consisting of: gaschromatograph (GC), liquid chromatograph (LC), high pressure liquidchromatograph (HPLC), a mass spectrometer (MS), a diffractometer, anUltraviolet-Visible (UV-VIS) spectrometer, a Infrared (IR) spectrometer,a Near Infrared (NIR) spectrometer, a Nuclear Magnetic Resonance (NMR)spectrometer, a viscosity meter or density meter.

Preferably, the analyser comprises on-line analyser or a samplecollection system, or a combination thereof.

Non-limiting examples of on-line analysers are a gas chromatograph (GC),liquid chromatograph (LC), high pressure liquid chromatograph (HPLC), amass spectrometer (MS), a diffractometer, an Ultraviolet-Visible(UV-VIS) spectrometer, a Infrared (IR) spectrometer, a Near Infrared(NIR) spectrometer, a Nuclear Magnetic Resonance (NMR) spectrometer, aviscosity meter, density meter. These analyzers may be equipped with asample valve or syringe injection system to allow injection of a smallrepresentative sample of the effluent stream.

As mentioned above also a sample collection system can be used for theanalysis of samples. In that case the samples are first collected incollection containers before being transferred to one or more analysers.Thus will allow more flexibility of the system, as it is not necessaryto integrate the analyser in the whole apparatus. The sample collectionsystem is designed in such a way that it can collect liquid samples incollection containers designed to collect liquids, or it can collectgaseous samples in collection containers designed to collect gas.Examples for liquid collection containers are reactor tubes, vials,wells or the like. Examples for gas collection containers aregas-collection bags (Tedlar bags), gas-tubes, gas pipettes, cold traps,cryogenic traps or the like. The collection containers may be organisedin a systematic way, such as for instance in a row, a matrix or acarrousel. Typical examples of such systems are reagent tube racks,96-well plates, 384-well plate, auto-sampler racks, or carrousel. Mostmodern analyser systems known in the art are equipped with a so-calledauto sampler allowing automatic analysis of a multitude of samples.Preferably the array of collection containers of such collection systemis configured in such a way that it is compatible with the auto-samplersof the consecutively used analyser system.

Typically the sample collection system is designed such that at a giventime the conduit for the diluted effluent stream is connected to onecollection container or to a waste stream. Preferably this connectionpoint is made in such a way that it is disconnectable allowing it toswitch between one and another collection container, or to switch from acollection container to a waste stream or visa versa. By having theability to switch between collection containers one is able to collectmore samples of one reactor at different moments in time. This willallow monitoring the catalyst performance as a function of time ormonitor its performance under different process conditions. An exampleof a disconnectable connection point is a tube or needle releasablyattached above the array of collection containers allowing drops ofliquid to fall in the individual collection containers. When a needle isused, the collection containers can either individually or collectivelybe sealed with a septum. The presence of such septum will avoidevaporation of the collected liquid and will suppress the negativeinfluence of air. For gas and liquid samples also multi-connectionvalves may be used to generate such disconnectable connection points.Also sample collection valves may be used, such as made by VICI (ValcoInstruments Co. Inc.).

Preferably the collection system should be fully automatic allowing itto change between collection containers, or between a collectioncontainer and a waste system in a automatic way. XY, or XY-Z robots orthe like are suitable for this and are commercially available as samplecollection robots. A typical manufacturer is Gilson Inc.

Additionally if desired, the collection containers may be conditioned byheating or cooling the system. Cooling may prove useful when sensitivesamples are collected that deteriorate at room temperature. Heating mayprove useful when solidification of crystallisation is to be avoided.

For use in high throughput experimentation where a multitude of reactorsis used the sample collection system can either be designed to collectsamples in a parallel or sequential way, or in a combination of both.The parallel approach is particular desired, although the sequential wayis also useful. In the sequential approach the effluent conduits of thevarious reactors are connected to a multi-selection valve, having twooutlets, viz. a selected steam outlet, and a common outlet. Variousexamples of such multi-selection valves are made by VICI. This valvewill allow selection of one of the streams of the individual reactors tobe guided to the sample collection system. The selected reactor effluentis then collected in one collection container. By proper synchronisationbetween the multi-selection valve and the sample collection system allreactor effluents can sequentially be sampled in the array of collectioncontainers.

In the parallel approach the multitude of effluent conduits of thevarious reactors are connected to a multitude of connection points.Preferably these connection points are needles or tube outlets assembledin an array. The spacing of the array should be such that the array ofneedles is compatible with the array of the collection containers. Inthis way a multitude of reactor effluents can be collectedsimultaneously in the array of collection containers. It will be clearto those skilled in the art that many different array configurationswill be possible. By making the connection points disconnectable it ispossible to switch the multitude of outlet of the diluted effluentconduit to more collection containers. This allows collection ofeffluents at different moments in time for a multitude reactor ofeffluents. By automating the movement of the array of outlets and themovement of the array of collection containers it will be possible tomake the system suitable for unattended operation.

The analyser may thus as well be a sample collector which can be used tocollect samples of the effluent stream, which samples can be analysed atanother location, if desired.

In a very attractive embodiment, the reactor assembly comprises aplurality of flow-through reactors as defined above. Most preferably,said flow-through reactors are arranged in parallel, therewith enablingthe performance of a plurality of parallel testing/screening reactions,wherein the effluent stream (i.e. the reaction products) of eachtesting/screening reaction can be analysed in parallel or, if desired,sequentially. In this respect, reference is made to the above identifiedWO 99/64160.

When the reactor assembly comprises a plurality of flow-throughreactors, the said assembly preferably comprises a selector valvebetween effluent conduits of multiple reactors and at least one analyserfor selectively connecting one of the said multiple reactors with thesaid analyser. By such an arrangement, sequential analyses of thereaction products of the different reactions, each carried out in adifferent reactor, can be analysed by the same analyser.

Such an apparatus is especially suitable for high-throughputexperimentation, wherein a large number of testing/screening reactions,using a plurality of reactors, optionally with different reactionconditions, are conducted simultaneously. In an alternative embodiment,it is also possible to connect the dilution fluid supply means directlydownstream of the selector valve. Further, when both a selector valveand one or more gas/liquid separators are used in combination, thegas/liquid separator may be placed either upstream or downstream of theselector valve. When placed downstream, a single separator is sufficientfor the gas/liquid separation from multiple reactors.

When the reaction in the reaction chamber occurs at elevated pressure,the apparatus may be equipped with one or more back-pressure regulators.Depending on the application and type of such back-pressure regulators,these can be placed at many different positions in the assembly, suchas, directly downstream of the reactor outlet, directly downstream ofthe gas/liquid separator or directly downstream of a multi-selectionvalve.

Back pressure regulators are used to control the pressure upstream ofthe regulator and are useful for generating and controlling the pressurein the reactor to a constant value at a wide range of flows. Typicalexamples of such back pressure regulators are given in WO 01/48575 andEP02075491.7

The skilled person will be able to determine the optimal position andthe suitable regulator type to be used in the reactor assembly.

The invention further relates to a process for analysing a fluideffluent stream from a flow-through reactor comprising a reactionchamber having a reaction zone, comprising the steps of:

-   -   A) diluting at least 30 w/w % of the effluent stream downstream        of the reaction zone with at least one dilution fluid,    -   B) transferring at least a portion of the diluted effluent        stream obtained in step A) to at least one analyser,    -   C) subjecting the transferred effluent stream to an analysis        procedure.

According to this embodiment of the invention, a significant portion ofthe effluent stream leaving the reaction chamber is diluted, i.e. atleast 30 w/w %, preferably at least 50 w/w %, more preferably at least80 w/w %, even more preferably at least 95 w/w % of the effluent streamis diluted; this is in particular the case when liquid components of theeffluent stream are to be analysed. In that case, most preferably thewhole liquid phase of the effluent stream is diluted. In case gaseouscomponents of the effluent stream are to be analysed, at least 30 v/v %,preferably at least 50 v/v %, more preferably at least 80 v/v %, evenmore preferably at least 95 v/v % of the effluent stream is diluted;most preferably the whole gaseous effluent stream is diluted in thatcase. This is in contrast to sampling methods, known in the art, whereinonly an insignificant small amount, i.e. less than 5 w/w % or 5 v/v %,of a reaction mixture is withdrawn from the reactor and diluted foranalysis. In this respect, reference is made to U.S. Pat. No. 6,178,830.

Such a process is in particular advantageous, when the reaction takingplace in the flow-through reactor is performed for analyses purposes,e.g. to establish optimal reaction conditions and for testing/screeningpurposes. As such reactors are preferably designed to be as small aspossible, the effluent stream is usually as low as 1 ml/min or less,preferably 0.5 ml/min or less. As it has been proven to be verydifficult to analyse such effluent streams with accuracy, in particularwhen the said stream comprises both gaseous and liquid components orother immiscible components, it is been found that diluting the wholeeffluent stream downstream of the reaction zone with a dilution fluidresults in a stream of larger volume that can be analysed with highaccuracy. The said diluted effluent stream, or at least a portionthereof, is transferred to at least one analyser, e.g. through aeffluent conduit as indicated above. It will be clear to the personskilled in the art, that not the whole diluted effluent stream has to betransferred to an analyser, but that a portion thereof may besufficient. Since most analytical equipment has a high sensitivity andreproducibility, it is possible to obtain very reproducible and accurateanalysis results, even at relatively high levels of dilution. Examplesof analysis procedures are indicated above.

It is to be noted that the diluted effluent stream can be splitted inmultiple streams, that can be transferred to different analysers to besubjected to multiple analyses procedures.

As mentioned above, with the process according to the present inventionit is e.g. possible to detect the mass flow rate of each individualcomponent in the liquid mixture and/or gas phase. This can beaccomplished by accurately recording the amount of diluent(s) added perunit of time. Now based on the concentration of the liquid components inthe diluted solution the production rate can be determined by:M _(x) =C _(x) ·M _(solvent)Where M_(x) is the molar flow of component X (mmole/minutes) exiting thereactor, C_(x) is the measured ratio between the concentration ofcomponent X in the solution (mmole/ml) and the concentration of thesolvent (mmole/ml). M_(solvent) is the molar flow of the solvent leadinginto the apparatus. To facilitate the calculation of M_(x) internalstandard may be added to the solvent with a pre-set concentration. Theexact determination of the concentration depends on that type ofanalyser used and is known to those skilled in the art.

In an attractive embodiment, the effluent stream is diluted in thereaction chamber, downstream of the reaction zone. As indicated above,the whole effluent stream can conveniently be diluted by introducing asingle dilution fluid stream into the reaction chamber. However, it isalso possible for the dilution fluid to be introduced into a conduit,transferring the effluent stream from the reaction chamber to e.g. ananalyser. However, in case multiple conduits are connected to thereaction chamber, the dilution fluid should preferably be introducedbefore the branching into the said multiple conduits, or be introducedinto each of such conduits in order to dilute the whole effluent stream.

Advantageously, a pre-selected amount of dilution fluid is supplied tothe effluent stream.

With a “pre-selected amount of dilution liquid” is meant such an amountthat is suitable to dilute the effluent stream to such an extent that asufficient amount of effluent stream is collected from the reactorallowing an accurate analysis to be performed. Usually, substantiallythe whole effluent stream will be collected. The pre-selected amount maybe in the form of a single pulse of dilution liquid, a discontinuousseries of pulses, but will preferably be in the form of a controlledand/or pre-determined continuous flow. Herewith measurements onconcentrations, fluxes and production rates can accurately be performed.

Preferably, a dilution fluid, in particular a liquid, is used providedthat the said fluid has no adverse effect on the effluent stream.However, a gaseous dilution fluid, or a combination of liquid andgaseous diluent fluids can be used, optionally provided via separatedilution fluid supply means. Preferably, the dilution fluid comprises apreferably inert liquid wherein the effluent stream is dissolved or atleast dispersed to generate a free flowing solution of at least theliquid components of the effluent stream. For the analyses of e.g.non-polar organic compounds, the dilution fluid may e.g. compriseheptane, toluene or butyl acetate, whereas for highly polar organiccompounds, e.g. methanol, acetic acid or water can be used. When agaseous dilution fluid is used it preferably has no adverse effects onthe effluent stream and/or on the analyser. Preferably it should bechemically inert and cheap. Preferably it also should not be the samegas as used in the reaction mixture, allowing the estimation of thedilution ratio by analysis of the gas composition of the dilutedeffluent.

The skilled person is however able to determine the proper (liquidand/or gaseous) dilution fluid to be used for the envisaged aim. Asoutlined above, the diluent fluid may also comprise a gas; theadvantages of using a gaseous dilution fluid are, among others:

-   -   a) By the addition of diluent gas, gaseous components exiting        the reaction zone will be swept to the analyser, making the        residence time in the downstream piping significantly shorter.        In this context the diluent will act as a purge gas.    -   b) By dilution by the purge gas the partial pressure of        components will be lowered. For components with a high vapour        pressure this allows keeping these components in the gas phase,        and avoid condensation. The lower partial pressure will also        lower the tendency to adsorb on the surface also leading to long        residence times.    -   c) By dilution by the purge gas and the resulting lower partial        pressure of the components exiting the reactor zone will lower        the chance of undesired consecutive reactions in the downstream        piping. For instance it is well known that reactive components        such as dienes or epoxides may react without the presence of a        catalyst.    -   d) When the flow rate of the dilution gas is monitored, it is        possible to calculate the production rate of the individual        gaseous components based on the concentration of the dilution        gas and the concentration of the individual gaseous component in        the effluent gas. This is even further facilitated by the        addition of an internal standard to the diluent at a known        concentration.    -   e) In case of a gas/liquid system exiting the reactor, the        addition of extra purge gas will facilitate the downstream        gas/liquid separation, especially when also liquid diluent is        added.        The advantages of a liquid diluent fluid are, among others:    -   a) Due to the addition of dilution liquid, liquid components        exiting the reaction zone will be swept to the analyser, making        the residence time in the downstream piping as short as        possible. The diluent will act as a purge liquid.    -   b) Due to the dilution by the purge liquid the concentration of        components with a high tendency to crystallise will be lowered        thus causing these components to stay in the liquid phase. The        lower concentration in the liquid phase of such components will        also lower the tendency to selectively adsorb to the surface.    -   c) The addition of dilution liquid will decrease the viscosity        of the liquid exiting the reactor zone.    -   d) In some particular cases the addition of dilution liquid will        allow extraction/scrubbing of gaseous components allowing a        simplified analysis of all component of the effluent stream.    -   e) The dilution with the dilution liquid and the resulting lower        concentration of the dissolved components exiting the reactor        zone will lower the chance of undesired consecutive reactions in        the downstream piping. For instance it is well known that        reactive components such as dienes or epoxides may react even        without the presence of a catalyst. In addition it is possible        to add quenching components (see also conditioning components)        in the diluent to avoid any consecutive reaction of        intermediates.    -   f) When the flow rate of the dilution liquid is monitored, it is        possible to calculate the production rate of the individual        gaseous components based on the concentration of the dilution        gas and the concentration of the individual gaseous component in        the effluent liquid. This is even further facilitated by the        addition of an internal standard to the diluent at a known        concentration (see below).    -   g) In case of a gas/liquid system exiting the reactor, the        addition of extra diluent liquid will facilitate the downstream        gas/liquid separation significantly.    -   h) It is easy to add an extra conditioning component to the        purging liquid. This conditioning component will react with the        reaction products, thus changing its chemical and physical        properties. This will improve the stability of these components,        and/or facilitate their sequential analysis.

As indicated above, the method according to the present invention isparticularly suitable for small scale reactors for performinganalytical, testing and screening reactions, wherein the effluentstream, when leaving the reaction zone has a liquid flow rate of below 1ml/min, in particular below 0.5 ml/min, and/or a gas flow rate of lessthan 100 Nml /min, in particular less than 50 Nml/min.

For the case where the effluent stream is diluted with a liquid diluent,the ratio in the diluted effluent stream, between volumetric diluentliquid flow: volumetric reactor liquid effluent flow is preferably0,2-10,000:1, more preferably 1-1,000:1 and most preferably 10-100:1.

For the case where the effluent stream is diluted with a gaseousdiluent, the ratio, in the diluted effluent stream, between volumetricdiluent gas flow; volumetric reactor gas effluent flow is preferablybetween 0,1 and 1000, more preferably 0,1-1,000:1, more preferably0,5-100:1, most preferably 10-1:1. By increasing the ratio, the samplingspeed is increased.

In both gas and liquid cases with too low dilution ratios no substantialadvantages of the diluent can be obtained. On the other hand a too highdilution ratio may result in unnecessary high diluent consumption and atoo dilute stream to allow proper and accurate analysis in the analyser.

The optimal ratio between the diluent and the effluent stream depends onseveral factors and will therefore vary depending on the type ofapplication. The upper limit of this ratio is often defined by thesensitivity of the analytical equipment or may be limited by e.g. thevial size of an auto collector robot. The lower limit is mainly definedby the solubility of the liquid components of the reactor effluent andby the rate, desired to transport the effluent liquid from the reactorto the analyser.

In a very attractive embodiment of the process according to theinvention, the diluted effluent stream is subjected to a gas/liquidseparation step before being subjected to the analysing procedure,providing a gaseous and a liquid effluent stream. Such a separation stepcan be performed using one or more gas/liquid separations, as describedabove. This embodiment is in particular relevant when the effluentstream, leaving the reaction zone comprises a liquid and a gaseouscomponent, or when a gaseous diluent is added to a liquid effluentstream or a liquid diluent is added to a gaseous effluent stream. Thepresence of liquid and gaseous components causes several problems in theanalyses procedures. For example, a slug of gas reactant, followed by aslug of liquid in the conduits wherein the effluent stream istransferred to e.g. an analyser, may cause pressure variation in theeffluent stream, resulting in a non-constant flow and to measurementinaccuracies. Further, the presence of gas and liquid may cause problemswith respect to pressure control by a downstream pressure regulator.

One of the most obvious problems caused by the presence of gas in theliquid is the fact that most liquid analysers can not cope with gasbubbles in the liquid stream. For GC or HPLC systems gas bubbles willcause a variation of the amount of liquid injected when using injectionvalves. In the inlet capillary of a MS it will cause strong fluctuationsand spectroscopic techniques such as UV-VIS, NIR or IR will stronglysuffer from the light scattering and liquid displacement when gasbubbles are present in the measuring cuvette, and even when trying tocollect the liquid with a auto-collector robot the presence of gas maylead to uncontrolled flow of liquid into the collection vials.

Another problem is the fact that very often one would like also to beable to measure the gas composition of the gas portion of the effluentstream. Although most of the above mentioned techniques can also beset-up to analyse gaseous samples, no analysers are known to exist thatmeasure both components within one instrument. To enable separateanalysis of gas and liquid on at least two separate analysers bothphases need to be separated first.

In addition, most gas analysers have large difficulties to cope withliquid droplets. In a GC it may ruin the column or injection valve, in aMS liquid may plug the inlet capillary and in spectroscopic techniquesit will interfere with the light beam and contaminate the cuvette.

Another problem when dealing with reactor effluents consisting of agas/liquid mixture is the fact that one also would be interested inmeasuring the production rate (mass flow) of both phases to be able toperform a proper mass balance over the reactor. The gas-liquidseparation step can be performed by gas/liquid separator devices thatare known in the art. By the addition of diluent(s) to the effluentstream the gas/liquid separation is highly facilitated. This is causedby the fact that the gas/liquid separator now can be designed for largervolumes allowing it to have a better separation and a lower relativefluid hold-up.

Preferably, both the gaseous and liquid effluent streams from aneffluent stream are separately subjected to an analysing procedure,enabling determination of both the gaseous and liquid components of theeffluent stream. However, if only the gaseous or the liquid componentsof the effluent stream are to be analysed, the other stream may bediscarded.

Preferably, the dilution fluid is supplied as a constant flow. Herewith,a fixed amount of dilution fluid is supplied. Thus, production rates canbe easily calculated from the concentrations of certain components inthe effluent stream based on mass balance, in particular when aninternal standard is incorporated (see below).

To obtain a proper mixture of the effluent stream and the dilutionfluid, the said effluent stream and dilution fluid may be properly mixedat the location wherein the stream and the fluid are combined.

An internal standard is particularly useful when the analyser is notable to detect the concentration of the diluent in the diluted effluent.This may be the case when the concentration of the diluent is too highcausing the analyser to run out of scale, or it may be that the diluentcannot be detected by the analyser. The concentration of the internalstandard can be chosen such that is in the same order of magnitude asthe concentration of the diluted reaction products in the dilutedeffluent.

When the internal standard is added to a liquid reaction mixture ordiluent, the internal standard used is preferably soluble in the saidreaction mixture or diluent liquid at its used concentration and itshould be easily detectable by the analyser when present in the dilutedeffluent stream mixture. Preferably it should have a low vapour pressureto avoid evaporation of the internal standard, and it should be inert tothe components of the reactor zone effluent. Those who are skilled inthe art will recognise that the proper choice of such internal standardwill largely depend on the application and on the analyser used. Someexamples for useful liquid internal standards are e.g. octane, xyleneand dibutylether.

The internal standard is preferably added before step c). Said internalstandard can be added to the reaction zone, e.g. together with thereactants and/or being incorporated in the dilution fluid. However,other ways of adding the internal standard are also possible, such as byseparately adding thereof in the effluent conduct(s). Also multipleinternal standards can be added, e.g. a combination of a liquid and agaseous standard, that may be added together or separately.

In some special cases one may additionally add one or more conditioningcompound(s) to the diluent fluid. This conditioning compound will reactwith one or more of the components of the reactor effluent, resulting inderivative components with a different chemical property such as forinstance a lower reactivity, higher stability or lower corrosiveness.Such method may also be used to generate components with differentphysical properties, such as lower viscosity, higher boiling point,lower boiling point, higher melting point or higher solubility. Suchchange of property may facilitate the downstream handling of thecomponents. Alike methods are well known in analytical chemistry andknown under the name of derivatizing agents. A typical example of suchconditioning compound is diazomethane that may react with non-volatileorganic acids to produce the far more volatile, more soluble and lesscorrosive methyl ester. Such conditioning compound should be present ata concentration high enough to convert all the components in the reactoreffluent to their corresponding conditioned derivative. Those who areskilled in the art will recognize that the choice of the conditioningcompound is strongly dependant of the application and the analyticalmethod. It will be clear that many different methods and compounds canbe used.

Also to gas diluent an internal standard can be added, with almost thesame functionality, use and constraints as with the liquid internalstandard. In contrast with the liquid internal standard preferably itshould have a high vapour pressure to avoid condensation of the internalstandard. Also it should not dissolve significantly in the liquiddiluent. Those who are skilled in the art will recognise that the properchoice of such internal standard will largely depend on the applicationand on the analyser used. Examples for useful internal standards aree.g. krypton, xenon, helium, carbon dioxide or methane.

The invention also relates to a process as described above, foranalysing the fluid effluent streams for a plurality of flow-throughreactors, each reactor comprising a reactor chamber having a reactionzone, comprising the steps of:

-   -   A) diluting at least 30 w/w % or at least 30 v/v % effluent        stream of each reactor downstream of the reaction zone with a        dilution fluid,    -   B) selectively transferring at least a portion of a first        effluent stream from a first reactor obtained in step A) to at        least one analyser,    -   C) subjecting the first transferred effluent stream to an        analysis procedure,    -   D) selectively transferring at least a portion of a second        effluent stream of a second reactor obtained in step A) to at        least one analyser,    -   E) subjecting the second transferred effluent stream to an        analysis procedure, and, optionally,    -   F) repeating steps D) and E) for any effluent stream of a        following reactor.

Such a process is particularly advantageous when multiple reactions arecarried out in parallel to test/screen for e.g. optimal reactionconditions. However, the above described sequential sampling method canalso be used in this process, although, for sampling procedures,parallel sampling as described above is preferred. When the reactionproducts, produced in the reaction zone of the reaction chamber areleaving the said reaction zone as effluent stream, the said significantportion of the effluent stream of each reactor is diluted. At least aportion of such a diluted effluent stream from one of the said reactorsis transferred to at least one analyser or optionally to a plurality ofanalysers, wherein is also possible that a portion of the said dilutedeffluent stream is discarded. In order to avoid the necessity to have aseparate analyser for each reactor, the effluent streams from themultiple reactors are selectively transferred to the analyser(s). Thismeans that the effluent stream from a first reactor is transferred toone or more analysers, whereas the effluent stream of other reactors arerefrained from being transferred or e.g. being stored in a buffercompartment for later analyses. As the transferred effluent stream hasbeen subjected to the analyses procedure in the analyser, the analyserwill be ready for a next analyses procedure of a following effluentstream. Then, at least a portion of a second effluent stream from asecond reactor can be transferred to the said analyser to be subjectedto the analyses procedure. These steps can be repeated until the desirednumber of effluent streams have been subjected to the envisaged analysesprocedures. The plurality of flow-through reactors can be arranged in aparallel manner, e.g. according to the teaching of WO 99/64160.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS 1 a-f show schematical cross sections of reactor assembliesaccording to the present invention;

FIGS. 2-5 are schematical diagrams of different embodiments of thereactor assembly according to the present invention; and

FIGS. 6, 7 and 8 show schematical diagrams of a reactor assemblyaccording to the present invention, comprising multiple reactors, aselector valve and a sample collector.

DETAILED DESCRIPTION OF THE INVENTION

In FIG. 1 a, a reactor assembly is shown, comprising a flow-throughreactor, comprising a reaction chamber 1, accommodating a reaction zone2, such as a catalytic fixed bed and an inlet 3 for inflow of at leastone of the reactants. The direction of the inflow is shown with arrow I.The reactor further comprises a first space 7, upstream of the reactionzone and a second space 8, downstream of the reaction zone. Thedownstream end of the reaction zone is in this case formed by a grid 9,holding the fixed catalytic bed in place. The reactor further comprisesan outlet 4 for an effluent stream from the reactor, the direction ofthe effluent stream being indicated with arrow III. The outlet 4 isconnected to an analyser 5 by an effluent conduit 6. Although a singleoutlet and a single effluent conduit is shown, the second space 8 maycomprise multiple outlets, each being connected to an effluent conduitand wherein each effluent conduit may be connected to an analyser.Further, dilution fluid supply means designed as a tubing 10 dischargein the reaction chamber, downstream of the reaction zone, in the secondspace 8. The direction of the flow of dilution fluid is indicated byarrow II.

In FIG. 1 b, a similar reactor assembly is shown, wherein the referencenumbers of FIG. 1 are used for similar or analogous features. Thedilution fluid supply means have a discharge opening 10, directing astream of dilution fluid towards to the bottom of the reactor bed. I.e.the downstream end of the reaction zone. The effluent conduit 6 branchesin conduits 6 a en 6 b, each of the said conduits being connected to ananalyser, 5 a and 5 b respectively.

In FIG. 1 c, the dilution fluid supply means enter the reaction chamberat the upstream side thereof, and being directed parallel to thedirection of the inflow I. The dilution fluid supply means 7 comprise anelongated tubing 11 entering the reaction chamber at the upstream sidethereof, said tubing extending through the first space 7 and reactionzone 2, having a discharge opening 10 a in the second space, close tothe downstream end of the reaction zone 2. Effluent conduit 6 branchesin conduit branch 6 a and 6 b respectively, conduit branch 6 a beingconnected to an analyser 5. Conduit branch 6 b may e.g. be connected toa waist outlet or a buffer vessel.

In FIG. 1 d, the reaction chamber 1 comprises reaction zone 2,substantially fully occupying the reaction chamber. The single reactoroutlet 4 is connected to analyser 5 by effluent conduit 6. In this case,the dilution fluid supply means 10 are connected to the effluent conduit6.

In FIG. 1 e a schematic cross-sectional view of an reactor arrangementaccording to the present invention is shown in partly assembled state.The system comprises a housing 1 for housing a plurality of essentiallytubular reaction chambers 2 having an inlet 13 and an outlet 18 at theopposite ends thereof. The reactors 2 may be embodied as tubes of metalor other suitable material.

The housing 1 comprises a base block 5 and a cover element 9. The baseblock 5 has a plurality of through going first channels 6 formed thereinfor removably housing the reactors 2. The cover element 9 is providedhere with third channels 15 each connecting to an inlet 13 of thereactor 2.

The first channels 6 are formed here as bores in the solid base block 5.However other designs, wherein a first channel 6 is entirely or partlyformed by a tubular part of the base block 5 are also possible.

The reactors 2 have a length such that each reactor 2 is entirelyaccommodated within the first channel 6.

It can be seen that an extension channel 25 is formed extending coaxialand in line with the first channel 6. The extension channel 25 extendsbetween the lower end of the first channel and the second face 8 of thebase block 5. The extension channel 25 has a smaller diameter than thefirst channel 6, so that an annular shoulder 26 is formed.

The reactor 2 can be designed to rest upon this annular shoulder 26.

A first face 7 of the base block 5 is facing towards the cover element9. The cover element 9 is releasable attachable on the first face 7 ofthe base block 5. There may be fastening means provided, such as screws,to attach the cover element 9 to the base block 5.

Between the first face 7 of the base block 5 and the bottom surface 10of the cover element 9, a number of high pressure resistant O-rings 11are provided as first sealing elements. These O-rings 11 are placed suchthat the O-ring 11 is near the inlet 13 of the first channel 6 andsurrounds this inlet 13. Hereby leakage between neighbouring firstchannels 6 is prevented.

As is shown, annular grooves are provided in the first face 7 of block 5for receiving the O-ring 11. This also prevents movement of the O-rings11 in case of a horizontal movement of the cover element 9.Alternatively, the annular grooves may be provided in the bottom surface10 of the cover element 9.

The housing 1 is further provided with resilient O-rings 12 acting assecond sealing elements. These O-rings 12 are located in the firstchannels 6 of the base block 5.

The reactors 2 each contain a reaction zone 17, for example containing acatalyst in the form of a catalyst bed.

The base block 5 comprises fourth channels 16 opening into zone 14, i.e.the space in first channel 6 outside the reactor 2 and below the secondsealing element 12, downstream of the reaction zone 17.

The fourth channels 16 can be used for example for purging or dilutingpurposes. For example the fourth channel 16 may be in fluidcommunication with a pressurised source of an inert fluid such as N₂, ormay be any other dilution fluid, that also may comprise a liquid.

To prevent condensing of the product obtained in the reactor zone 17, ifa gaseous product is obtained, an inert gas such as N₂ can be fed byfourth channel 16 to force the product obtained in the experimentthrough the outlet 18 of first channel 6. Herewith a very easy dilutingof the product gas can be obtained and condensing can be prevented.

In a possible application of the system of FIG. 1 e, a fluid to betreated is fed via third channel 15 to the inlet 3 of the vessel 2. Thisthird channel 15 will of course usually be provided with further sealingmeans or valves to prevent the fed fluid from returning to the thirdchannel 15. After passing the reactor zone 17 the treated fluid willenter the zone 14 and be discharged via outlet 18.

In practice second channels 16 are preferably used for feeding dilutionfluid, such as a gaseous dilution fluid whereas third channels 15 arepreferably used for feeding reactants to the reaction, such as liquid,but possibly also gaseous reactants. For the feeding of a liquid forinstance, a capillary may be used, which may be partially inserted inthe third channel 15. In this arrangement any dilution fluid passingthrough channel 16 is subjected to temperature conditioning as thereactants in the reaction zone.

The assembly furthermore shows the possibility to arrange a dilutionfluid conduit 28 such that it extends into the extension channel 25. Afourth sealing means 29 is provided in this example to seal the annulargap between the second fluid conduit 28 and the base block 5.

The second fluid conduit 28 could be designed as a capillary, e.g. forfeeding a liquid dilution fluid into the space below the vessel 2, i.e.without entering the temperature conditioned reaction zone. The dilutedeffluent stream can be removed via the extension channel 25. When aconduit 28 is present, conduit 16 an be absent or be used for otherpurposes, e.g. for adding conditioning fluid, without diluent fluid.

In the arrangement according to FIG. 1 f, a liquid dilution fluid supplymeans 10 enters the reactor 1, the diluent fluent supply means having adischarge opening, close to grid 9 and directing a stream of dilutionliquid towards the said grid. Effluent conduit 6 enters a gas/liquidseparator 15, comprising a chamber 550 having an outlet 6 b fortransporting a representative portion of the liquid effluent to ananalyser (not shown). Outlet 6 a transports all the gaseous effluent andany remainder of liquid effluent. Chamber 550 may be equipped withmixing elements (not shown). The liquid diluent, discharged from theliquid diluent supply means 10, contacts grid 9, therewith mixing withthe liquid components of the effluent stream, leaving the reaction zone2. The mixture of liquid dilution fluid and the liquid components of theeffluent stream (droplets 800) are collected in chamber 550 of thegas/liquid separator 15. A representative portion of the liquidcomponents of the effluent stream, mixed with the liquid diluent fluid,leaves the gas/liquid separator 15 via outlet 6 b, whereas the gaseouscomponents and any remainder of liquid effluent leave the gas/liquidseparator 15 via outlet 6 a. In this arrangement, chamber 550 also actsas mixing and buffer chamber.

It is to be understood that the arrangements of the effluent conduitsand reaction chambers of FIGS. 1 a-f can be interchanged among oneanother. It is however to be understood that the arrangement of thedilution fluid supply means (10 in FIGS. 1 a-d and f, and 26 and/or 28in FIG. 1 e) may discharge both in the second space and/or in theeffluent conduits when a second space is present in the reactionchamber. When the reaction chamber does however not comprise such asecond space, e.g. as in FIG. 1 d, it is preferred to have the dilutionfluid supply means connected to the effluent conduit, which will beillustrated in the following drawings.

It is to be understood that in the conduits, means for controlling theflow can be present, such as pressure regulators, flow restrictors,filters or check valves. Typical examples for a flow restrictor areneedle valves, capillaries, filters or orifices.

Further, a gas/liquid separator can be present in the effluent conduits.Also means for buffering and additional mixing can be present. A typicalbuffering and mixing system is a vessel or other system with a lowlength to diameter ratio. Also static mixers can be used.

In FIG. 2, a simple arrangement of the assembly according to theinvention is schematically shown. Reactor 11 comprises a reactor outlet4, being connected to an effluent conduit 6, which is connected toeffluent conduit 10. The dilution fluid is stored in container 12.Effluent conduit 6 comprises a pressure regulator 13, and branches intoconduit branch 6 a and 6 b. Conduit branch 6 a is connected to ananalyser 5. Conduit branch 6 b can be connected to another analyser orcan be used as waste outlet (not shown). The dotted arrow 14 indicatesan alternative connection of the dilution fluid supply means to effluentconduit 6 downstream of the pressure regulator In most cases addition ofdiluent fluid upstream of the pressure regulator is preferred, as itwill facilitate the function of the pressure regulator. However, in somecases addition downstream of the pressure regulator is preferred, forinstance when one is not capable in pressurising the dilution fluid. Onemay also decide to have one diluent upstream of the pressure regulatorand one other diluent fluid downstream of the pressure regulator.

In FIG. 3, the same reference numbers are used as in FIG. 2 for similaror analogous features; in this case, a gas/liquid separator 15 ispresent in conduit 6, separating the gaseous components of the effluentstream, transferred to the effluent conduit 6 into effluent conduit 61for gaseous components and effluent conduit 62 for liquid components.Effluent conduit 62 is connected to a liquid analyser 52; in theeffluent conduit 62, a pump 16 is present. Conduit 61 branches intoconduit 61 a, being connected to gas analyser 5, and into conduit 61 b.In FIG. 4, a similar assembly as in FIG. 3 is shown, wherein the liquidanalyser is a sample collection robot 53.

In FIG. 5, an assembly corresponding to that of FIG. 3 is shown, whereinthe pressure regulator 13 is now located downstream of the gas liquidseparator 15. As now the gas liquid separator is operated at a highpressure, pump 16, may now be replaced by a flow regulating device suchan orifice, a capillary, a mass flow controller or a needle valve.

FIG. 6 shows a reactor assembly comprising reactors 111, 112, 113 and114, having outlets 41, 42, 43 and 44 respectively, being connected to aselector valve 17 by effluent conduits 611, 612, 613 and 614respectively. Features already discussed in previous figures havecorresponding reference numbers.

The dilution fluid supply means 10 are connected to each of the effluentconduits 611, 612, 613 and 614 of which only the connection witheffluent conduit 614 is shown. Alternatively, the dilution fluid supplymeans can be connected to effluent conduit 6, downstream of the selectorvalve 17, therewith obviating the necessity for connection to each ofthe effluent conduits upstream of the selection valve; this indicated bydotted arrow 14. Further, effluent conduit 6 is connected to agas/liquid separator 15 according to the assembly of FIG. 5.

An alternative embodiment is shown in FIG. 7, wherein the assemblycomprises reactors 111 and 112, each being connected to a multiple valve17 by effluent conduits 611 and 612 respectively. Effluent conduits 611and 612 are connected to dilution fluid supply means 101 and 102respectively, being fed from buffer vessels 121 and 122 respectively.Preferably the buffer vessels 121 and 122 are one and the same. Dilutionfluid supply means 101 and 102 may each comprise of a capillary of equallength and diameter leading to an equal flow to each effluent conduit;also other flow constricting means, known in the art may be used forthis function. Effluent conduits 611 and 612 are connected each to aseparate gas/liquid separator 151 and 152 respectively, the gas/liquidseparator 152 separating the liquid effluent and the gaseous effluentinto effluent conduits 632 and 622 respectively. Effluent conduit 622 isconnected to the selector valve 17, whereas effluent conduit 632 isconnected to a liquid analyser. Accordingly, effluent conduit 611 isconnected to gas/liquid separator 151, separating the gaseous and liquidcomponents of the effluent stream to effluent conduits 621 and 631respectively. Effluent conduit 621 is connected to the selector valve,whereas effluent conduit 631 is connected to a liquid analyser. Theselector valve is further connected to conduits 650 and 660, eachcomprising a pressure regulator 131 and 132 respectively. Conduit 660branches, downstream of the pressure regulator 132 to conduit 661 andconduit 662. Conduit 662 is connected to a gas analyser. Those who areskilled in the art will recognise that the concept shown in FIG. 7 caneasily be extrapolated to more than two reactors, by simply multiplyingall the components.

In FIG. 8, an assembly arrangement similar to that of FIG. 7 is shown,wherein however each effluent stream is connected to two seriallyarranged gas/liquid separators (151 a, 151 b and 152 a, 152 brespectively). In the upstream gas/liquid separators 151 a and 152 a, arepresentative amount of liquid is separated from the effluent streamand analysed by a liquid sample collector 52 b. Downstream of separator151 a and 152 a, separators 151 b and 152 b are arranged, receiving theeffluent mixture comprising the gas and still also liquid of theoriginal effluent stream. In the said separators 151 b and 152 b, arepresentative amount of gas is separated and analysed in gas analyser5. The not separated residual effluent mixture is discarded from theassembly through vents 700 a and 700 b respectively.

FIG. 9 shows a liquid sample collector in more detail, comprising eightconducts (1-8) for transporting the liquid to be analysed, wherein eachconduct is connected to needles 901 for discharging the liquid incollection containers 903. The needles 901 are held by a robot arm 902that can be automatically or manually moved, so that the liquid,dispensed from a needle, can be dispensed in a plurality of containers903.

Referring to the above figures, the action of the assembly according tothe present invention as well as the method of the invention will befurther explained.

Referring to FIG. 1, a fluid inflow, comprising at least one reactant isentered in the reaction chamber and is subjected to a chemical reactionin the reaction zone 2. As the effluent stream from the reaction zoneenters the space 7 in the reaction chamber 1, downstream of the reactionzone, the said effluent stream is contacted with the dilution fluid,introduced into the said space by the dilution fluid supply means 10. Inspace 8, mixing/dilution of the effluent stream in the dilution fluidtakes place, where upon the mixture/dilution is further transferred tothe analyser 5 through effluent conduit 6. In case the dilution fluidsupply means are connected to the effluent conduit 6 and not dischargingin the reaction chamber, the effluent stream is contacted with thedilution fluid in the effluent conduit. In order to obtain propermixing, the effluent conduit may comprise mixing elements, such asstatic mixing elements, however, the effluent stream and the dilutionfluid can be contacted to one another and mixed without the aid ofmixing devices. The effluent conduit may comprise a back-pressureregulator, as is shown in FIG. 2. Downstream or upstream of the pressureregulator, a gas/liquid separator can be present in the effluentconduit, separating the gaseous components of the effluent conduit fromthe liquid components thereof. The liquid components are transferred toliquid analyser 52 with the aid of a pump 16. However, any other deviceknown in the art can be used for transport of the liquid from thegas/liquid separator 15 to the liquid analyser 52. In a specialembodiment, the conduit connecting the gas/liquid separator and theliquid analyser comprises a capillary. This configuration is highlysuitable when operating at elevated pressures. Due to the pressuredifference over the capillary a small stream of liquid will be createdexiting the gas/liquid separator and entering the liquid analyser. Thecapillary system has the advantage that is low cost, easy to install andhighly robust, allowing it to operate at very high pressures.

As indicated before, the liquid analyser may also comprise of a samplecollection system, such as a parallel sample collector, as describedabove and further illustrated in FIG. 9.

The gaseous components of the effluent are further transferred to a gasanalyser 5. Any surplus of gaseous components may be discarded viaconduit 6 b. However, said conduit may also be connected to a second gasanalyser. In the multi-reactor configuration of FIG. 6, multiplereactors 111-114 are connected, via a selector valve and a gas/liquidseparator to the analysers, analysing the effluent streams of therespective reactors. In order to analyse the different effluent streams,originating from the different reactors, the selector valve connects oneof the effluent conduits 611-614 to conduit 6, therewith blockingpassage of the effluent streams from the other effluent conduits toconduit 6. As indicated above, the effluent stream is diluted either inthe conduit connecting the reactor to the selector valve (conduit611-614) or in conduit 6. The effluent stream, passing through theselector valve can be analysed as indicated above by a liquid analyser52 and a gas analyser 5. After proper analyses, the connection betweenone of the effluent conduits 611-614 and conduit 6 is closed by theselector valve and another effluent conduit, originating from afollowing reactor is connected to conduit 6, therewith enabling analysesof the effluent stream, originating from the said reactor. This processcan be repeated until all effluent streams are analysed. If desired,multiple analyses of each reactor can be performed. The effluent streamsof reactors, that are blocked by the selector valve are led to a wasteoutlet (not shown). The skilled person will be aware of proper choiceand positioning of such a waste outlet.

The selector valve can also be positioned in the reactor assembly afterseparation of the gaseous from the liquid components from the effluentstreams. In the arrangement, shown in FIG. 7, the selector valve isconnected to conduits, transferring gaseous components from differentreactors to the gas analyser. The gas/liquid separation and analysis ofliquid components is performed upstream of the said selector valve bygas/liquid separators 151 and 152, and sample collectors 52A and 52Brespectively; however, it is also possible to introduce an additionalselector valve, connecting e.g. conduits 631 and 632 for liquidcomponents of the different effluent streams, to a single liquidanalyser, connected downstream to the said second selector valve.

It is also possible to connect outlets 631 and 632 to a parallel samplecollection system allowing simultaneous collection of the dilutedselection stream.

In FIG. 8, the effluent stream from reactor 111 enters gas/liquidseparator 151 a, wherein a representative portion of the liquid effluentstream is separated and passed to liquid sample collector 52 b. Thegaseous effluent stream, possibly still containing a portion of theliquid components of the effluent stream (not separated by the separator151 a) enters gas/liquid separator 151 b, wherein a representativeportion of the gaseous components of the effluent stream are separatedand passed to gas analyser 5 via multi selector valve 17. Not separatedresidual effluent mixture is passed to vent 700 b. Accordingly, theeffluent stream from reactor 112 is passed to gas/liquid separators 152a and 152 b respectively, whereas the not separated residual effluentmixture thereof is discarded through vent 700 a. In this arrangement,gas/liquid separators of a relatively simple design can be used, as thegaseous/liquid mixture of the effluent stream does not have to becompletely separated in a quantitative manner, as indicated above.

EXAMPLES

The reduction of 3-hexen-2-on to 3-hexen-2-ol was performed both in gasphase as in trickle flow mode. A fixed reaction pressure of 10 bar and areaction temperature of 100° C. was chosen in both cases. The saturatedvapour pressure of 3-hexen-2-ol at 100° C. is approximately 20 kPa andat 25° C. it is 0.3 kPa.

Example: 1 Reduction of 3-hexen-2-on to 3-hexen-2-ol in the Gas Phase

The reactor set-up as shown in FIG. 1 e and FIG. 7 without however thepresence of a gas/liquid separator and a liquid analyser. The equipmentwas equipped 64 reactors in parallel with one GC.

A library of heterogeneous catalysts with a wide variation in chemicalcomposition was loaded in the reactors. The amount of catalyst was 100μg per individual reactor. 5 Nml/min/reactor (0.2 mmol/min/reactor) ofhydrogen gas and 0.004 mmol/min 3-hexen-2-on liquid feed was fed to eachreactor. Thus the gas in the reaction zone may just consist of 2 v %3-hexen-2-ol.

The reaction mixture flowing out of the reactor was led through tracedlines to the GC analyser. To increase speed to the analyzer and preventcondensation the reactor mixture exiting the reaction zone was dilutedwith 50 Nml/min/reactor nitrogen, where the gas was added according toFIG. 1E. To measure all reaction mixtures rotary selection valves areused. For accurate measurements internal and external standards wereused. 1 v % of helium (internal standard 1) was fed together with thehydrogen and 1 v % of cyclohexane (internal standard 2) was fed togetherwith the 3-hexen-2-on.

The GC peaks were integrated and the ratio between the individualcomponents and the internal standards were calculated. From this theproduction rate and the conversion, selectivity and yield could becalculated. See table 1.

Example 2: Reduction of 3-hexen-2-on to 3-hexen-2-ol in the TricklePhase

By adding significantly more 3-hexen-2-on the majority of the reactantwill remain in the liquid phase, causing the reactant to trickle throughthe catalyst bed. The term “trickle phase” means that a mixture of gasand liquid is fed to a reaction zone, wherein the liquid passes(trickles) through the said zone by gravity force. In this experiment a3-hexen-2-on feed of 0.083 mmole/min/reactor (20 times more then in thepreceding example) was used. To the outlet of each reactordi-isopropylether diluent was added at 100 mg/min/reactor using a pumpand a distributor with capillaries. The diluent contained 0.0.085 mole %of hexadecane internal standard. The hexadecane flow rate was 0.83micromole/min. To the liquid reactor feed also 1 vol % heptadecane wasadded as an internal standard. This internal standard together with thehexadecane standard allows us to monitor the ratio of the reactant flowrate and the diluent flow rate for each individual reactor. Also a gasdiluent was added consisting of 10 Nml/min/reactor nitrogen with 0.44vol % of He.

For the liquid diluent addition, gas diluent addition and gas/liquidseparation a set-up was used as described in FIGS. 1E, 8 and 9. Thegas/liquid separator has a dimension of approximately 0.5 ml, whichgives a good separation in a gas/liquid stream and a liquid stream. Theseparation block with the gas/liquid separators was cooled to roomtemperature to optimise gas/liquid separation. The liquid stream wascollected with a robotic fraction collector in GC vials, for lateroff-line analysis. The system resembles the system of FIG. 9 but then 64outlets were used instead of 8. Every hour 64 new GC vials were placedunder the liquid effluent outlet.

The gas/liquid stream from the separator flows to the selection valves.The selected stream is then led over a second gas liquid separator,which separates the selected stream in a gas-liquid and a gas flow. Thenthe pressure of the remaining gas flow is reduced to atmosphericpressure from which the online GC takes samples.

The GC peaks of both the liquid phase and the gas phase were integratedand the ratio between the individual components and the internalstandards were calculated. From this the production rate and theconversion, selectivity and yield could be calculated. See table 2.

TABLE 1 Concentration relative to internal standard Reactor Time C6H10OC6H11OH C6H13OH C6H14 Calculated catalyst performance number measured3-hexen-2on 3-hexen-2-ol 3-hexanol hexane H2 C6H10O C6H11OH C6H13OHC6H14 C6H11OH (−) Catalyst (−) (hr min) (mol/mol (l)st) (mol/mol (l)st)(mol/mol (l)st) (mol/mol (l)st) (mol/mol (g)st) conversion (%) yield (%)yield (%) yield (%) selectivity (%) 1 AVCat1 09:00 111.80 2.58 0.50 0.00101.14 3.0 2.2 0.4 0.0 73.7 2 AVCat2 09:10 17.49 59.67 37.13 −0.29 98.6884.8 51.8 32.2 −0.3 61.0 3 AVCat3 09:20 25.45 20.05 22.58 46.44 97.6177.9 17.4 19.5 40.3 22.3 4 AVCat4 09:30 108.90 7.01 0.57 −1.04 101.117.3 6.1 0.5 −0.9 83.5 5 AVCat5 09:40 91.91 11.31 3.88 6.80 100.51 20.39.8 3.4 5.9 48.3 6 AVCat6 09:50 67.97 48.46 0.43 0.00 100.37 41.0 40.30.4 0.0 98.2 7 AVCat7 10:00 109.99 4.13 0.07 0.00 101.13 4.6 3.6 0.1 0.077.7 8 AVCat8 10:10 25.54 35.93 0.95 51.44 97.83 77.9 31.2 0.8 44.6 40.09 AVCat9 10:20 84.71 21.67 5.87 1.41 100.54 29.5 18.8 5.1 1.2 70.8 10AVCat10 10:30 45.03 47.33 18.15 4.25 99.51 60.9 41.0 15.7 3.7 67.4 11AVCat11 10:40 102.90 2.65 3.48 4.57 100.79 10.8 2.3 3.0 4.0 21.3 12AVCat12 10:50 69.78 3.41 37.98 2.25 99.69 39.5 3.0 32.9 1.9 7.5 13AVCat13 11:00 25.82 73.58 11.20 3.21 99.35 77.6 63.8 9.7 2.8 82.2 14AVCat14 11:10 43.12 68.08 0.94 2.46 99.84 62.6 59.0 0.8 2.1 94.3 15AVCat15 11:20 103.60 2.67 7.35 0.00 100.90 10.2 2.3 6.4 0.0 22.8 16AVCat16 11:30 39.19 24.68 8.07 41.47 98.30 66.0 21.4 7.0 36.0 32.4 17AVCat17 11:40 71.77 2.41 40.98 0.00 99.72 37.8 2.1 35.5 0.0 5.5 18AVCat18 11:50 110.51 2.87 0.34 1.37 101.07 4.2 2.5 0.3 1.2 60.0 19AVCat19 12:00 38.17 23.55 18.47 34.84 98.30 68.9 20.4 16.0 30.2 30.5 20AVCat20 12:10 41.41 8.49 20.66 44.41 97.99 64.1 7.4 17.9 38.5 11.5 21AVCat21 12:20 40.34 7.93 43.57 21.74 98.39 65.0 6.9 37.8 18.9 10.6 22AVCat22 12:30 39.95 20.13 23.61 31.22 98.37 65.3 17.5 20.5 27.1 26.7 23AVCat23 12:40 84.00 28.60 1.86 −0.49 100.68 27.1 24.8 1.6 −0.4 91.4 24AVCat24 12:50 8.36 33.88 60.96 10.36 97.92 92.7 29.4 52.9 9.0 31.7 25AVCat25 13:00 101.35 8.33 0.30 4.27 100.82 12.1 7.2 0.3 3.7 59.7 26AVCat26 13:10 112.13 2.64 0.36 −0.87 101.19 2.8 2.3 0.3 −0.8 83.0 27AVCat27 13:20 14.44 40.08 53.17 6.91 98.27 87.5 34.7 46.1 6.0 39.7 28AVCat28 13:30 36.84 0.37 30.72 46.58 97.66 68.1 0.3 26.6 40.4 0.5 29AVCat29 13:40 14.52 74.97 19.81 5.59 98.89 87.4 65.0 17.2 4.8 74.4 30AVCat30 13:50 7.52 6.44 13.46 86.23 96.07 93.5 5.6 11.7 74.8 6.0 31AVCat31 14:00 29.19 78.16 3.34 4.53 99.47 74.7 67.8 2.9 3.9 90.8 32AVCat32 14:10 49.74 45.93 7.17 11.67 99.52 56.9 39.8 6.2 10.3 70.1 33AVCat33 14:20 50.45 28.70 19.17 15.62 99.21 56.2 24.9 16.6 13.5 44.3 34AVCat34 14:30 2.15 10.41 43.79 57.69 96.44 98.1 9.0 38.0 50.0 9.2 35AVCat35 14:40 93.77 16.27 2.92 1.76 100.72 18.7 14.1 2.5 1.5 75.6 36AVCat36 14:50 105.24 7.40 0.88 0.98 100.99 8.7 6.4 0.8 0.9 73.6 37AVCat37 15:00 47.45 65.71 1.06 −0.82 100.05 58.8 57.0 0.9 −0.7 96.8 38AVCat38 15:10 14.04 28.05 28.58 44.04 97.38 87.8 24.3 24.8 38.2 27.7 39AVCat39 15:20 90.93 4.19 5.64 12.60 100.26 21.1 3.6 4.9 10.9 17.2 40AVCat40 15:30 84.04 5.63 8.25 15.77 99.98 27.1 4.9 7.2 13.7 18.0 41AVCat41 15:40 75.76 0.09 27.83 9.79 99.71 34.3 0.1 24.1 8.5 0.2 42AVCat42 15:50 95.26 2.44 9.73 6.31 100.48 17.4 2.1 8.4 5.5 12.2 43AVCat43 16:00 79.50 15.89 3.36 15.24 100.00 31.1 13.8 2.9 13.2 44.4 44AVCat44 16:10 81.94 24.83 6.78 0.00 100.53 28.9 21.5 5.9 0.0 74.4 45AVCat45 16:20 89.03 14.37 11.10 0.48 100.53 22.8 12.5 9.6 0.4 54.7 46AVCat46 16:30 0.12 55.15 4.44 53.61 97.25 99.9 47.8 3.9 46.5 47.9 47AVCat47 16:40 11.67 49.15 47.95 5.99 98.34 89.9 42.6 41.6 5.2 47.4 48AVCat48 16:50 71.93 17.60 2.83 20.94 99.69 37.6 15.3 2.5 18.2 40.6 49AVCat49 17:00 47.74 58.49 8.16 0.26 99.87 58.6 50.7 7.1 0.2 86.6 50AVCat50 17:10 107.24 5.11 1.07 0.97 101.02 7.0 4.4 0.9 0.8 63.4 51AVCat51 17:20 103.15 6.23 0.16 4.89 100.83 10.5 5.4 0.1 4.2 51.3 52AVCat52 17:30 48.55 58.59 3.65 3.59 99.65 57.9 50.8 3.2 3.1 87.8 53AVCat53 17:40 56.44 2.03 16.49 39.61 98.50 51.0 1.8 14.3 34.4 3.4 54AVCat54 17:50 50.26 28.91 5.45 30.00 98.92 56.4 25.1 4.7 26.0 44.4 55AVCat55 18:00 25.31 67.58 12.49 8.20 99.14 78.1 58.6 10.8 7.1 75.1 56AVCat56 18:10 6.46 45.82 39.14 21.97 97.86 94.4 39.7 33.9 19.1 42.1 57AVCat57 18:20 37.33 12.01 17.93 47.63 97.85 67.6 10.4 15.6 41.3 15.4 58AVCat58 18:30 69.85 39.20 0.61 4.33 100.26 39.4 34.0 0.5 3.8 86.3 59AVCat59 18:40 96.66 16.41 1.48 −1.19 100.92 16.2 14.2 1.3 −1.0 88.0 60AVCat60 18:50 31.97 28.52 13.50 40.43 98.10 72.3 24.7 11.7 35.1 34.2 61AVCat61 19:00 100.15 12.18 0.36 1.14 100.91 13.1 10.6 0.3 1.0 80.4 62AVCat62 19:10 79.03 4.06 32.10 0.00 100.00 31.5 3.5 27.8 0.0 11.2 63AVCat63 19:20 85.42 3.68 9.39 16.46 99.94 25.9 3.2 8.1 14.3 12.3 64 none19:30 115.30 0.00 0.00 0.00 101.20 0.0 0.0 0.0 0.0

TABLE 2 Concentration relative to internal standard Reactor Time C6H10OC6H11OH C6H13OH C6H14 Calculated performance number measured H23-hexen-2on 3-hexen-2-ol 3-hexanol hexane C6H10O C6H11OH C6H13OH C6H14C6H11OH (−) Catalyst (−) (hr min) (mol/mol (g)st) (mol/mol (l)st2)(mol/mol (l)st2) (mol/mol (l)st2) (mol/mol (l)st2) conversion (%) yield(%) yield (%) yield (%) selectivity (%) 1 AVCat65 09:00 92.42 92.06 0.412.16 5.37 7.9 0.4 2.2 5.4 5.2 2 AVCat66 09:10 11.88 3.80 31.56 12.5151.13 96.2 31.6 13.5 51.1 32.8 3 AVCat67 09:20 58.91 58.35 11.17 2.1828.27 41.6 11.2 2.2 28.3 26.8 4 AVCat68 09:30 17.24 15.47 9.47 35.4139.65 84.5 9.5 35.4 39.6 11.2 5 AVCat69 09:40 90.31 87.65 2.21 6.17 3.7712.1 2.2 8.2 3.8 18.2 6 AVCat70 09:50 76.22 42.96 55.61 0.23 1.01 57.055.8 0.2 1.0 97.8 7 AVCat71 10:00 62.34 37.42 39.52 16.46 6.60 82.6 39.315.3 5.5 63.2 8 AVCat72 10:10 24.15 6.04 21.24 56.56 18.16 94.0 21.256.6 16.2 22.6 9 AVCat73 10:20 98.72 97.25 0.04 2.29 0.42 2.8 0.0 2.30.4 1.4 10 AVCat74 10:30 93.99 13.08 3.88 5.00 1.08 86.9 3.9 5.0 1.1 4.511 AVCat75 10:40 84.93 61.98 37.46 0.55 0.01 38.0 37.5 0.5 0.0 98.5 12AVCat76 10:50 64.15 55.23 8.70 28.99 7.08 44.8 8.7 29.0 7.1 19.4 13AVCat77 11:00 51.95 23.15 42.03 29.63 5.19 76.9 42.0 29.6 5.2 54.7 14AVCat78 11:10 30.66 30.47 24.67 39.31 5.55 69.5 24.7 39.3 5.5 35.5 15AVCat79 11:20 31.68 1.10 15.38 60.60 9.46 98.9 15.4 60.6 9.5 15.6 16AVCat80 11:30 65.03 65.15 0.01 18.68 16.16 34.6 0.0 18.7 16.2 0.0 17AVCat81 11:40 72.19 37.29 59.36 0.56 2.79 62.7 59.4 0.6 2.8 94.7 18AVCat82 11:50 78.46 73.46 3.03 19.58 3.93 26.5 3.0 18.6 3.9 11.4 19AVCat83 12:00 85.59 73.22 21.64 0.03 5.12 26.8 21.6 0.0 5.1 60.8 20AVCat84 12:10 84.00 75.20 13.08 7.44 4.28 24.8 13.1 7.4 4.3 52.7 21AVCat85 12:20 88.87 82.50 8.98 8.98 1.44 17.4 7.0 9.0 1.4 40.1 22AVCat86 12:30 59.37 42.86 33.95 4.28 18.94 57.1 33.9 4.3 18.9 59.4 23AVCat87 12:40 92.24 87.66 6.73 1.72 3.70 12.1 6.7 1.7 3.7 55.4 24AVCat88 12:50 94.75 92.56 0.59 5.85 1.01 7.4 0.6 5.8 1.0 8.0 25 AVCat8913:00 −1.82 13.85 5.28 3.43 77.45 88.2 5.3 3.4 77.4 6.1 26 AVCat90 13:1082.47 62.82 30.68 5.72 0.78 37.2 30.7 5.7 0.8 82.5 27 AVCat91 13:2055.91 7.58 83.38 3.12 5.96 92.4 83.4 3.1 6.0 90.2 28 AVCat92 13:30 78.6982.92 25.33 7.15 4.60 37.1 25.3 7.2 4.6 68.3 29 AVCat93 13:40 7.86 4.0430.29 5.88 59.83 96.0 30.3 5.9 59.8 31.5 30 AVCat94 13:50 63.01 41.8828.60 26.52 2.99 58.1 28.6 26.5 3.0 49.2 31 AVCat95 14:00 93.77 89.886.34 0.05 3.73 10.1 8.3 0.1 3.7 62.6 32 AVCat96 14:10 64.57 58.45 13.4811.00 17.07 41.8 13.5 11.0 17.1 32.4 33 AVCat97 14:20 72.38 63.69 17.804.93 13.57 36.3 17.8 4.9 13.6 49.0 34 AVCat98 14:30 37.27 2.30 52.9035.58 9.22 97.7 52.9 35.6 9.2 54.1 35 AVCat99 14:40 81.47 68.45 19.109.65 2.81 31.6 19.1 9.6 2.8 60.5 36 AVCat100 14:50 17.36 18.86 8.8026.86 45.48 81.1 8.8 25.9 45.5 10.8 37 AVCat101 15:00 48.33 42.91 20.430.20 36.47 57.1 20.4 0.2 36.5 35.8 38 AVCat102 15:10 66.28 32.68 54.4310.24 2.65 67.3 54.4 10.2 2.7 80.9 39 AVCat103 15:20 87.71 70.28 19.084.75 5.89 29.7 19.1 4.8 5.9 64.2 40 AVCat104 15:30 43.64 25.99 38.438.58 27.00 74.0 38.4 8.6 27.0 51.9 41 AVCat105 15:40 48.72 34.12 25.8321.44 18.60 65.9 25.8 21.4 18.6 39.2 42 AVCat106 15:50 56.25 29.83 48.2811.77 10.04 70.1 48.3 11.8 10.0 68.9 43 AVCat107 16:00 55.71 29.50 48.2511.03 13.21 70.5 48.2 11.0 13.2 65.6 44 AVCat108 16:10 55.41 22.73 55.5012.15 9.62 77.3 55.5 12.1 9.6 71.8 45 AVCat109 16:20 44.89 33.45 29.826.38 30.35 68.5 29.8 6.4 30.4 44.8 46 AVCat110 16:30 50.14 5.35 78.755.27 10.63 94.6 78.7 5.3 10.6 83.2 47 AVCat111 16:40 76.29 42.16 57.100.21 0.53 57.8 57.1 0.2 0.5 98.7 48 AVCat112 16:50 50.12 43.09 6.4436.85 13.82 56.9 6.4 36.7 13.8 11.3 49 AVCat113 17:00 93.99 91.65 0.796.37 1.20 8.4 0.8 6.4 1.2 9.4 50 AVCat114 17:10 55.13 48.98 7.07 29.6114.34 51.0 7.1 29.6 14.3 13.9 51 AVCat115 17:20 65.17 50.13 19.53 25.075.28 49.9 19.5 25.1 5.3 39.2 52 AVCat116 17:30 56.61 59.94 2.29 9.7728.00 40.1 2.3 9.8 28.0 5.7 53 AVCat117 17:40 17.19 21.49 17.77 0.6260.11 78.5 17.8 0.6 60.1 22.6 54 AVCat118 17:50 76.56 61.17 22.08 13.862.89 38.8 22.1 13.9 2.9 56.9 55 AVCat119 18:00 49.17 41.41 19.63 13.0425.92 58.6 19.6 13.0 25.9 33.5 56 AVCat120 18:10 88.57 70.87 25.36 1.951.82 29.1 25.4 2.0 1.6 87.0 57 AVCat121 18:20 60.02 35.79 47.18 0.5916.46 64.2 47.2 0.6 16.5 73.4 58 AVCat122 18:30 48.46 37.34 15.84 31.1615.66 62.7 15.8 31.2 15.7 25.3 59 AVCat123 18:40 89.82 87.19 0.45 10.521.84 12.8 0.5 10.5 1.8 3.5 60 AVCat124 18:50 52.77 48.31 10.80 16.5222.37 51.7 10.8 18.5 22.4 20.9 61 AVCat125 19:00 83.93 73.05 19.43 1.016.51 26.9 19.4 1.0 6.5 72.1 62 AVCat126 19:10 61.73 35.29 36.92 26.641.15 64.7 36.9 26.6 1.1 57.1 63 AVCat127 19:20 67.64 29.38 62.22 7.840.58 70.6 62.2 7.8 0.6 88.1 64 none 19:30 101.20 100.00 0.00 0.00 0.000.0 0.0 0.0 0.0

1. A reactor assembly comprising: at least one flow-through reactor forperforming at least one chemical reaction, the flow-through reactorcomprising: a reaction chamber, comprising a reaction zone, the reactionchamber being connected to at least one reactor inlet for at least onereactant, upstream of the reaction zone, and to at least one reactoroutlet for the effluent stream from the reaction zone, downstream of thereaction zone, at least one analyser for subjecting the effluent streamto an analysing procedure, each reactor outlet being connected to saidat least one analyser by an effluent conduit, wherein the reactorassembly comprises: at least one dilution fluid supply means, for addingat least one dilution liquid to the effluent stream, downstream of thereaction zone, a base block having a plurality of reactor chamberchannels therein, each reactor chamber channel being accessible from afirst face of the base block; a releasable cover element that covers thefirst face of the base block in operation of the reactor assembly; aplurality of tubular reaction chambers, each tubular reaction chamberhaving an inlet and an outlet at the opposite ends thereof, each tubularreaction chamber being accommodated within a corresponding reactionchamber channel of the base block and being removable therefrom; thecover element being provided with a plurality of reactant feed channelseach in communication with an inlet of a tubular reaction chamber; afirst sealing element being disposed between the first face of the baseblock and the cover at each first channel; and a second sealing elementbeing disposed in the first channel between each tubular reactionchamber and the base block so as to separate an upstream portion of thereaction chamber channel in open communication with the reaction chamberinlet from a downstream portion of the reaction chamber channel in opencommunication with the reaction chamber outlet; wherein for eachreaction chamber channel an effluent channel is formed in the baseblock, which effluent channel extends from the downstream portion ofreaction chamber channel to a second face of the base block; and whereinthe reactor assembly further includes a plurality of diluent fluidsupply channels, each in fluid communication with a downstream portionof a reaction chamber channel.
 2. Reactor assembly for analysing theeffluent stream from at least one flow-through reactor, comprising: atleast one flow-through reactor for performing at least one chemicalreaction, the reactor comprising: a reaction chamber, comprising areaction zone, the reaction chamber being connected to at least onereactor inlet for at least one reactant, upstream of the reaction zone,at least one reactor outlet for the effluent stream from the reactionzone, downstream of the reaction zone, wherein the reactor assemblyfurther comprises: a feed conduit that is in fluid communication withthe reactor inlet, upstream of the reaction zone, for feeding a reactantto the reaction chamber, an effluent conduit, which comprises aneffluent conduit inlet and an effluent conduit outlet, wherein theeffluent conduit inlet is in fluid communication with the reactoroutlet, a gas/liquid separator, that has a gas/liquid separator inlet, agas outlet and a liquid outlet, wherein the gas/liquid separator inletis in fluid communication with the effluent conduit outlet, at least oneanalyser, for subjecting at least a part of the effluent to an analysingprocedure, the analyser being arranged downstream of the gas/liquidseparator, and at least one dilution liquid supply means, for adding atleast one dilution liquid to the effluent stream, which dilution liquidsupply means is in fluid communication with the reaction chamber or tothe effluent conduit, wherein the connection of the dilution liquidsupply means to the reaction chamber or to the effluent conduit is at alocation downstream of the reaction zone and upstream of the gas/liquidseparator.
 3. Reactor assembly according to claim 2, wherein thedilution liquid supply means is connected to the reaction chamber or tothe effluent conduit at a location which is at most 10 mm from thedownstream end of the reaction zone.
 4. Reactor assembly according toclaim 2, wherein the analyser is in fluid communication with the gasoutlet of the gas/liquid separator.
 5. Reactor assembly according toclaim 2, wherein the analyser is in fluid communication with the liquidoutlet of the gas/liquid separator.
 6. Reactor assembly according toclaim 2, wherein the reactor assembly further comprises a samplecollection system for receiving effluent from the gas outlet and/orliquid outlet of the gas/liquid separator.
 7. Reactor assembly accordingto claim 2, wherein the dilution liquid supply means comprises flow ratecontrol means, which flow rate control means are set such that the ratioin the diluted effluent stream, between volumetric diluent liquid flow:volumetric reactor liquid effluent flow is 0.2-10000:1, more preferably1-1000:1 and most preferably 10-100:1.